Fungicidal compositions

ABSTRACT

Synergistic fungicidal compositions comprising (i) a substituted 1-hydroxyethyl-triazole of the formula ##STR1## in which R 1 , R 2 , X, Y and A have various meanings, or addition products thereof with acids or metal salts, and (ii) at least one of 
     (A) wettable sulphur, 
     (B) a polyhalogenoalkylthio derivative, 
     (C) a guanidine derivative, 
     (D) an aromatic acid lactone, 
     (E) a dithiocarbamate, 
     (F) a benzimidazole derivative, 
     (G) an imidazole or triazole derivative, 
     (H) a phosphoric acid ester, 
     (I) a tetrahydroquinoline derivative, 
     (J) an S,N-heterocyclic compound, 
     (K) a urea derivative, 
     (L) a sulphonamide derivative, 
     (M) a polyhydroxyether derivative, 
     (N) a triazine derivative, 
     (O) a copper-hydroxy quinoline complex, 
     (P) an N-formul derivative, 
     (Q) a morpholine derivative, 
     (R) a quinoxaline derivative, and 
     (S) a dicarboxamide derivative.

This is a division of application Ser. No 161,578, filed February 29,1988, now U.S. Pat. No. 4,849,440, which is a continuation ofapplication Ser. No. 864,068, filed May 16, 1986, now abandoned, whichis a division of application Ser. No. 644,749, filed August 27, 1984,now U.S. Pat. No. 4,623,653.

The present invention relates to new fungicidal active compoundcombinations of special known substituted 1-hydroxyethyl-triazolylderivatives and other known fungicidal active compounds.

It is generally known that mixtures containing 1,2,4-triazolederivatives, such as, for example,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone, incombination with other known fungicides have a substantially greateraction than the individual components. See U.S. Ser. No. 307,336 filedSeptember 30, 1981, now U.S. Pat. No. RE 31,693. However, the activityof the active compound mixtures is not completely satisfactory in allfields of use.

It has been found that new active compound combinations of specialsubstituted 1-hydroxyethyl-triazolyl derivatives of the formula ##STR2##in which R¹ represents chlorine, phenyl, methoximinomethyl or1-methoximinoethyl,

R² represents hydrogen, methyl or chlorine,

X and Y are identical or different and represent hydrogen, fluorine orchlorine and

A represents the grouping --OCH₂ --, and also represents the grouping--CH₂ CH₂ -- when X and/or Y represent fluorine or chlorine,

and their acid addition salts and metal salt complexes and

(A) wettable sulphur and/or

(B) polyhalogenoalkylthio derivatives of the formulae ##STR3## and/or(C) a guanidine derivative of the formula ##STR4## and/or (D) anaromatic carboxylic acid derivative of the formula ##STR5## and/or (E)dithiocarbamates of the formulae ##STR6## and/or (F) benzimidazolederivatives of the formulae ##STR7## and/or (G) derivatives ofimidazoles and triazoles of the formulae ##STR8## and/or (H) aphosphoric acid ester of the formula ##STR9## and/or (I) atetrahydroquinoline derivative of the formulae ##STR10## and/or (J)S,N-heterocyclic compounds of the formulae ##STR11## and/or (K) a ureaderivative of the formula ##STR12## and/or (L) a sulphonamide derivativeof the formula ##STR13## and/or (M) a polyhydroxyether derivative of theformula ##STR14## and/or (N) a triazine derivative of the formula##STR15## and/or (O) a copper complex salt of the formula ##STR16##and/or (P) an N-formyl derivative of the formula ##STR17## and/or (Q)morpholine derivatives of the formulae ##STR18## and/or (R) aquinoxaline derivative of the formula ##STR19## and/or (S) adicarboximide derivative of the formulae ##STR20## have a particularlyhigh fungicidal activity.

Surprisingly, the fungicidal action of the active compound combinationsaccording to the invention is substantially higher than the action ofthe individual components and, where relevant, than the sum of theindividual components (synergistic effect). The discovery of thesecombinations of special compounds of the formula (I) and the activecompounds of the abovementioned groups (A), (B), (C), (D), (E), (F),(G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R) and (S) thusrepresents a valuable enrichment of the art.

Formula (I) above gives an unambiguous definition of the substituted1-hydroxyethyl-triazolyl derivatives specially to be used for thecombination according to the invention; this formula preferably embracesthe following compounds:

(Ia) R¹ =Cl, R² =H, X=F, Y=H, A=--CH₂ CH₂ --

(Ib) R¹ =CH₃ ON=CH--, R² =H, X=H, Y=H, A=--OCH₂ --

(Ic) R¹ = ##STR21## R² =H, X=H, Y=H, A=--OCH₂ -- (Id) R¹ =Cl, R² =CH₃,X=H, Y=H, A=--OCH₂ --

(Ie) R¹ =Cl, R² =CH₃, X=F, Y=H, A=--OCH₂ --

(If) R¹ =Cl, R² =Cl, X=F, Y=H, A=--OCH₂ --

(Ig) R¹ =Cl, R² =H, X=F, Y=F, A=--CH₂ CH₂ --

(Ih) R¹ =CH₃ ON=C (CH₃)--, R² =H, A=--OCH₂ --

The stated compounds of the formula (I) have been described; see U.S.Ser. No. 260,479 filed May 4, 1981, now abandoned, Ser. Nos. 458,086filed January 14, 1983 and 534,233 filed September 21, 1983, both nowpending.

The compounds which are to be used as components for the mixture andwhich belong to the abovementioned groups (A), (B), (C), (D), (E), (F),(G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R) and (S) havebeen described in the literature; in this context, see the followingreferences:

(A): R. Wegler, `Chemie der Pflanzenschutz- undSchadlingsbekampfungsmittel` (Chemistry of Plant Protection Agents andPest-Combating Agents), Volume 2, page 51, Springer Verlag BerlinHeidelberg/New York, 1970;

(B): R. Wegler, loc. cit., pages 95, 108, 109 and 110;

(C): R. Wegler, loc. cit., page 70;

(D): K. H. Buchel, `Pflanzenschutz und Schadlingsbekampfung``(PlantProtection and Pest-Combating`, page 146, Georg Thieme Verlag,Stuttgart, 1977;

(E): R. Wegler, loc. cit., pages 65 and 66;

(F): DE-AS (German Published Specification) 1,209,799, DE-OS (GermanPublished Specification) 1,932,297, U.S. Patent Specification No.3,010,968;

(G): DE-AS (German Published Specification) 2,201,063, DE-AS (GermanPublished Specification) 2,324,010, DE-OS (German PublishedSpecification) 2,063,857, DE-AS (German Published Specification)2,429,523, DE-OS (German Published Specification) 3,018,866;

(H): R. Wegler, loc. cit., page 132;

(I): German Patent Application No. P 32 34 529 of 17.9.1982 [leA 21962], U.S. Pat. No. 3,917,838;

(J): DE-OS (German Published Specification) 2,250,077, DE-OS (GermanPublished Specification) 2,062,348;

(K): DE-OS (German Published Specification) 2,732,257;

(L): K. H. Buchel, loc, cit., page 142;

(M): Chem. Commun. 1972, No. 12, pages 747-748;

(N): R. Wegler, loc. cit., page 120;

(O): R. Wegler, loc. cit., page 112;

(P): R. Wegler, loc. cit., page 97

(Q): K. H. Buchel; loc. cit., page 149; DE-OS (German PublishedSpecification) 2,656,747;

(R): R. Wegler, loc. cit., page 128 and

(S): K. H. Buchel, loc. cit., page 148.

Preferred active compound combinations are those comprising thesubstituted 1-hydroxyethyl-triazolyl derivatives of the formula (Ia),(Ib), (Ic), (Id), (Ie), (If), (Ig) or (Ih) and

an active compound of the formulae (IIa), (IIb), (IIc) or (IId);

and/or

an active compound of the formula (III);

and/or

an active compound of the formula (IV);

and/or

an active compound of the formulae (Va), (Vb), (Vc) or (Vd);

and/or

an active compound of the formulae (VIIe);

and/or

an active compound of the formula (VIII);

and/or

an active compound of the formula (IXa);

and/or

an active compound of the formula (Xa);

and/or

an active compound of the formula (XI);

and/or

an active compound of the formula (XII);

and/or

an active compound of the formula (XIII).

An active compound combination consisting of the2,2-bisfluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-3-pentanols ofthe formula (I) and the active compound from the groups (A) and/or (B)and/or (C) and/or (D) and or (E) and/or (F) and/or (G) and/or (H) and/or(I) and/or (J) and/or (K) and/or (L) and/or (M) and/or (N) and/or (O)and/or (P) and/or (Q) and/or (R) and/or (S) can also contain furtheractive compounds (for example as a third component).

The weight ratios of the active compound groups in the active compoundcombinations can vary within relatively wide ranges. In general, 0.01 to500 parts by weight of active compound from the active compound classes(A) to (S), preferably 0.02 to 200 parts by weight of the latter,particularly preferably 0.1 to 50 parts by weight, are employed per partby weight of the compound of the formula (I).

The active compound combinations according to the invention exhibit apowerful microbicidal action and can be employed in practice forcombating undesired microorganism; they are suitable for use as plantprotection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compound combinations, atthe concentrations required for combating plant diseases, permitstreatment of above-ground parts of plants, of vegetative propagationstock and seeds, and of the soil.

The active compound combinations according to the invention have a verybroad spectrum of action and can be used against parasitic fungi whichinfect above-ground parts of plants or attack the plants through thesoil, as well as against seed-borne pathogens. Such active compoundcombinations are of particular practical importance as seed dressingsagainst phytopathogenic fungi which are borne with the seed or occur inthe soil and infect the crop plants from there. The diseases in-volvedare seedling diseases, root rots and stalk, stem, leaf, bloom, fruit andseed diseases, which are caused, in particular, by Tilletia, Urocystis,Ustilago, Septoria, Typhula, Rhynchosporium, Helminthosporium andFusarium species. As a result of the systemic action of one of thecomponents of the mixture, the plants are also often protected, for arelatively long time after dressing, from pathogens which can attackvarious parts of the shoot, for example powdery mildew fungi and rustfungi. In addition, the active compound combinations can also beemployed as soil-treatment agents against phytopathogenic fungi, and areeffective against root rots and Tracheomycoses which are caused by, forexample, pathogens of the genera pythium, Verticillium, Phialophora,Rhizoctonia, Fusarium and Thielaviopsis.

However, when applied to the above-ground parts of plants, the activecompound combinations according to the invention also exhibit anexcellent action against pathogens on various crop plants, such aspowdery mildew fungi (Erysiphe, Uncinula, Sphaerotheca and Podosphaeraspecies an Leveillula taurica), rust fungi, Venturia species, Cercosporaspecies, Alternaria species, Botrytis species, Phytophthora species,Peronospora species, Fusarium species, Pyrenophora species, Cochliobolusspecies, Septoria species, Pseudocercosporella herpotrichoides,Pyricularia oryzae and Pellicularia sasakii.

The active compounds can be converted to customary formulations such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, natural and synthetiic materials impregnated with activecompound, very fine capsules in polymenic substances and in coatingcompositions for seed, and formulation used with burning equipment, suchas fumigating cartridges, fumigating cans, fumigating coils and thelike, as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is , liquid solvents,liquefied gases under pressure, and/or solid carriers, optionally withthe use of surfaceactive agents, that is, emulsifying agents and/ordispersing agents, and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or gylcol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellant, such ashalognated hydrocarbons as well as butane, propane, nitrogen and carbondixide; as solid carriers there are suitable: for example ground naturalminerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, and ground synthetic miinerals,such as highly-dispersed silicic acid, alumina and silicates; as solidcarriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emlsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas poloxysethylene-fatty aced esters, polyoxyethylene-fatty alcoholethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkylsulphates, asryl sulphonates as well as albumin hydrolysis products; asdispersing agents therre are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and naturalphospholiplids, such as cephalins and lecithins, and syntheticphospholipids lipids can be used in the formulations. Further additivescan be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as slats of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain bestween 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations or in the various use forms as a mixture with other knownactive compounds, such as fungicides, bactericides, insecticides,acaricides, nematicides, herbicides, bird repellents, growth factors,plant nutrients an agents for improving soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared there by further dilution, suchas ready-to-use solutions, emulsions, suspensions, powders, pastes andgranules. They are used in the customary manner, for example bywatering, immersion, spraying atomizing, misting, vaporizing, injecting,forming a slurry, brushing on, dusting, scattering, dry dressing, moistdressing wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, perferably 0.001 to 0.02% by weight, are required at theplace of action.

The following use examples serve as illustrations.

EXAMPLE A:

Pyricularia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable perparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for preparative activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried, the plants are inoculated with an aqueius sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In order to demonstrate a synergistic effect between the activecompounds used in these test the results were evaluated by the methoddescribed by R. S. Colby (Calculating Synergistic and AntagonisticResponses of Herbicide Combinations: Weeds 15 20-22, 1967). The expectedinfestation, in %, of the untreated control (E) was calculated inaccordance with the equation

    E=X·y/100

In this equation, X and Y denote the disease infestation expressed as a% of the untreated control--which is permitted by the two preparationswhen applied separately. A synergistic effect is present when thefungicidal action of the active compound combinations is greater thanthat of the individual active compounds applied. In this case, theinfestation actually observed must be less than the value for theexpected infestation (E), calculated from the formula given above.

                  TABLE A                                                         ______________________________________                                         Pyricularia test (rice)/protective                                           ______________________________________                                                       Active com- Disease infestation                                               pound concen-                                                                             as a % of the un-                                  Active compound                                                                              tration in %                                                                              treated control                                    ______________________________________                                        (Ia) (known)   0.0025      20                                                                0.001       50                                                 (Ib) (known)   0.0025      50                                                                0.001       70                                                 (IV) (known)   0.001       70                                                 (TETRACHLOROPH-                                                                              0.0005      90                                                 THALIDE)                                                                      (XII) (known)  0.001       50                                                 (PROBENAZOLE)  0.0005      70                                                 (VIIe) (known) 0.001       70                                                 (PROCHLORAZ)   0.0005      70                                                 (IXa) (known)  0.001       50                                                                0.0005      90                                                 ______________________________________                                                                           Expected                                                            Observed  infestation                                                         infestation                                                                             of (E) after                                              Active    after appli-                                                                            application                                               compound  cation of of the                                                    concen-   the mixture                                                                             mixture                                                   tration   as a % of the untreated                              Active compound                                                                              in %      control                                              ______________________________________                                        Mixture of (Ia) and (XII)                                                                    0.0025    10        14                                         (mixing ratio 5:1)                                                                           +0.0005                                                        Mixture of (Ia) and (XII)                                                                    0.001     10        25                                         (mixing ratio 1:1)                                                                           +0.001                                                         Mixture of (Ia) and (XII)                                                                    0.001     15        35                                         (mixing ratio 2:1)                                                                           +0.0005                                                        Mixture of (Ia) and (IXa)                                                                    0.001     20        25                                         (mixing ratio 1:1)                                                                           +0.001                                                         Mixture of (Ia) and (IXa)                                                                    0.001     40        45                                         (mixing ratio 2:1)                                                                           +0.0005                                                        Mixture of (Ib) and (IV)                                                                     0.0025    20        35                                         (mixing ratio 2.5:1)                                                                         +0.001                                                         Mixture of (Ib) and (VIIe)                                                                   0.001     30        49                                         (mixing ratio 1:1)                                                                           +0.001                                                         Mixture of (Ib) and (VIIe)                                                                   0.001     30        49                                         (mixing ratio 2:1)                                                                           +0.0005                                                        ______________________________________                                    

EXAMPLE B

Pellicularia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for activity, young rice plants in the 3 to 4 leaf stage aresprayed until dripping wet. The plants remain in a greenhouse until theyhave dried off. The plants are then inoculated with Pellicularia sasakiiand are placed at 25° C. and 100% relative atmospheric humidity.

The evaluation of the disease infestation is carried out 5 to 8 daysafter the inoculation.

In order to demonstrate a synergistic effect between the activecompounds used in these tests, the results were evaluated by the methoddescribed by R. S. Colby (Calculating Synergistic and AntagonisticResponses of Herbicide Combinations: Weeds 15, 20-22, 1967). Theexpected infestation, in %, of the untreated control (E) was calculatedin accordance with the equation

    E=X·Y/100

In this equation, X and Y denote the disease infestation--expressed as a% of the untreated control--which is permitted by the two preparationswhen applied separately. A synergistic effect is present when thefungicidal action of the active compound combination is greater thanthat of the individual active compounds applied. In this case, theinfestation actually observed must be less than the value for theexpected infestation (E), calculated from the formula given above.

                  TABLE B                                                         ______________________________________                                         Pellicularia test (rice)/protective                                          ______________________________________                                                       Active                                                                        compound                                                                      concen-   Disease infestation                                                 tration   as a % of the                                        Active compound                                                                              in %      untreated control                                    ______________________________________                                        (Ia) (known)   0.0025    20                                                                  0.001     30                                                                  0.0005    100                                                  (Ib) (known)   0.0025    50                                                   (XI) (known)   0.0001    70                                                   (PENCYCURON)                                                                  (XIII) (known) 0.001     30                                                   (VALIDAMYCIN)  0.0005    70                                                   ______________________________________                                                                 Observed  Expected                                                            infestation                                                                             infestation                                                         after appli-                                                                            after appli-                                                        cation of cation of                                                           the mixture                                                                             the mixture                                                         as a % of the untreated                                                       control                                              ______________________________________                                        Mixture of (Ia) and (XI)                                                                     0.0025    10        14                                         (mixing ratio 25:1)                                                                          +0.0001                                                        Mixture of (Ia) and (XI)                                                                     0.001     10        21                                         (mixing ratio 10:1)                                                                          +0.0001                                                        Mixture of (Ia) and (XI)                                                                     0.0005    40        70                                         (mixing ratio 5:1)                                                                           +0.0001                                                        Mixture of (Ia) and (XIII)                                                                   0.0025    10        14                                         (mixing ratio 5:1)                                                                           +0.0005                                                        Mixture of (Ia) and (XIII)                                                                   0.001     10        21                                         (mixing ratio 2:1)                                                                           +0.0005                                                        Mixture of (Ib) and (XIII)                                                                   0.0025    10        15                                         (mixing ratio 2.5:1)                                                                         +0.001                                                         Mixture of (Ib) and (XIII)                                                                   0.0025    10        35                                         (mixing ratio 5:1)                                                                           +0.0005                                                        ______________________________________                                    

EXAMPLE C

Sphaerotheca test (cucumber)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are dusted with conidia of the fungusSphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23° to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

                  TABLE C                                                         ______________________________________                                        Sphaerotheca test (cucumber)/protective                                                            Infestation in % in the                                                       case of an active                                                             compound concen-                                         Active compound      tration of                                               ______________________________________                                        Wettable sulphur (known)                                                                           0.0025       60                                          (VIIa) (known)       0.000025     67                                          (TRIADIMEFON)                                                                 (Ic) (known)         0.00005      75                                                               0.000025     87                                          (Ia) (known)         0.00005      63                                                               0.000025     57                                          Mixture of (Ic) and wettable sulphur                                                               0.00005      18                                          (mixing ratio 1:50)  0.0025                                                   Mixture of (Ia) and wettable sulphur                                                               0.00005      16                                          (mixing ratio 1:50)  +0.0025                                                  Mixture of (Ic) and (VIIa)                                                                         0.000025     45                                          (mixing ratio 1:1)   +0.000025                                                Mixture of (Ia) and (VIIa)                                                                         0.000025     30                                          (mixing ratio 1:1)   +0.000025                                                ______________________________________                                    

EXAMPLE D

Erysiphe test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound 1 part by weight ofactive compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In order to demonstrate a synergistic effect between the activecompounds used in these tests, the results were evaluated by the methoddescribed by R. S. Colby (Calculating Synergistic and AntagonisticResponses of Herbicide Combinations: Weeds 15, 20-22, 1967). Theexpected infestation, in %, of the untreated control was calculated inaccordance with the equation

    E=X·Y/100

In this equation, X and Y denote the disease infestation--expressed as a% of the untreated control--which is permitted by the two preparationswhen applied separately. A synergistic effect is present when thefungicidal action of the active compound combination is greater thanthat of the individual active compounds applied. In this case, theinfestation actually observed must be less than the value for theexpected infestation (E), calculated from the formula given above.

                  TABLE D                                                         ______________________________________                                         Erysiphe test (barley)/protective                                            ______________________________________                                                    Active compound                                                                            Disease infest-                                                  concentration in                                                                           ation as a %                                                     the spray liquor                                                                           of the untreated                                     Active compound                                                                           in % by weight                                                                             control                                              ______________________________________                                        (Ib) (known)                                                                              0.00025      100                                                  (Vd) (known)                                                                              0.025        51.9                                                 (PROPINEB)                                                                    ______________________________________                                                                 Observed  Expected                                                            infest-   infestation                                                         ation after                                                                             (E) after                                                           application                                                                             application                                                         of the mix-                                                                             of the mix-                                                         ture      ture                                                                as a % of the untreated                                                       control                                              ______________________________________                                        Mixture of (Ib)                                                                           0.00025      16.2      51.9                                       and (Vd)    0.025                                                             (mixing ratio 1:100)                                                          ______________________________________                                    

EXAMPLE E

Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound 1 part by weight ofactive compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In order to demonstrate a synergistic effect between the activecompounds used in these tests, the results were evaluated by the methoddescribed by R. S. Colby (Calculating Synergistic and AntagonisticResponses of Herbicide Combinations: Weeds 15, 20-22, 1967). Theexpected infestation, in %, of the untreated control was calculated inaccordance with the equation

    E=X·Y/100

In this equation, X and Y denote the disease infestation--expressed as a% of the untreated control--which is permitted by the two preparationswhen applied separately. A synergistic effect is present when thefungicidal action of the active compound combination is greater thanthat of the individual active compounds applied. In this case, theinfestation actually observed must be less than the value for theexpected infestation (E), calculated from the formula given above.

                  TABLE E                                                         ______________________________________                                         Leptosphaeria nodorum test/(wheat) protective                                ______________________________________                                                   Active compound                                                               concentration                                                                              Disease infest-                                                  in the spray ation as a % of                                                  liquor in % by                                                                             the untreated                                         Active compound                                                                          weight       control                                               ______________________________________                                        (Ia) (known)                                                                             0.01         32.5                                                  (Ib) (known)                                                                             0.01         50.0                                                  (IId) (known)                                                                            0.01         82.5                                                  (CAPTAFOL)                                                                    (Xb) (known)                                                                             0.025        50.0                                                  (FLUBENZI-                                                                    MINE)                                                                         (XIV) (known)                                                                            0.005        64.8                                                  (ANILAZIN)                                                                    ______________________________________                                                                Observed  Expected                                                            infesta-  infesta-                                                            tion after                                                                              tion (E)                                                            application                                                                             after appli-                                                        of the mix-                                                                             cation of the                                                       ture      mixture                                                             as a % of the untreated                                                       control                                               ______________________________________                                        Mixture of (Ia)                                                                          0.01         25.0      26.8                                        and (IId)                                                                     (mixing ratio                                                                            +0.01                                                              1:1)                                                                          Mixture of (Ia)                                                                          0.01          0.0      16.3                                        and (Xb)                                                                      (mixing ratio                                                                            +0.025                                                             1:2.5)                                                                        Mixture of (Ib)                                                                          0.01         25.0      41.3                                        and (IId)                                                                     (mixing ratio                                                                            +0.01                                                              1:1)                                                                          Mixture of (Ib)                                                                          0.01         25.0      32.4                                        and (XIV)                                                                     (mixing ratio                                                                            +0.005                                                             2:1)                                                                          ______________________________________                                    

EXAMPLE F

Drechslera graminea test (barley)/seed treatment (syn. Helminthosporiumgramineum)

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the infected seed is shaken with the dressing ina closed glass flask for 3 minutes.

The seed is embedded in sieved, moist standard soil and is exposed to atemperature of 4° C. in closed Petri dishes in a refrigerator for 10days. Germination of the barley, and possibly also of the fungus spores,is thereby initiated. 2 batches of 50 grains of the pregerminated barleyare subsequently sown 3 cm deep in standard soil and are cultivated in agreenhouse at a temperature of about 18° C., in seedboxes which areexposed to light for 15 hours daily.

About 3 weeks after sowing, the plants are evaluated for symptoms ofstripe disease.

                  TABLE F                                                         ______________________________________                                        Drechslera graminea test (barley)/seed treatment                              (syn. Helminthosporium gramineum)                                                                          Diseased                                                          Amount of   plants as a                                                       active com- % of the total                                                    pound applied                                                                             number of                                                         in mg/kg of plants which                                     Active compound  seed        have emerged                                     ______________________________________                                        not treated with the dressing                                                                  --          33.7                                             (Ib) (known)     20          11.8                                             (VIIc) (known)   100         11.6                                             BITERTANOL                                                                    Mixture of (Ib) and (VIIc)                                                                     20          0.0                                              (mixing ratio 1:5)                                                                             +100                                                         ______________________________________                                    

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. A fungicidal composition comprising a synergisticfungicidally effective amount of a mixture of a compound of the formula##STR22## or an addition product thereof with an acid or metal salt, and(ii) a dithiocarbamate of the formula ##STR23## (Va) R¹ =H, M=Zn (Vb) R¹=H, M=Mn(Vc) mixture of (Va) and (Vb) (Vd) R¹ =CH₃, M=Zn,the weightratio of (i):(ii) ranging from about 1:0.1 to 1:100.
 2. A fungicidalcomposition according to claim 1, wherein the weight ratio of (i):(ii)is between about 1:0.1 and 1:50.
 3. A process for combating fungicomprising applying to such fungi or to their habitat a fungicidallyeffective amount of a composition according to claim
 1. 4. A fungicidalcomposition according to claim 2, wherein (ii) is ##STR24##